CN1134343C

Movatterモバイル変換

Info

Publication number: CN1134343C
Application number: CNB998069221A
Authority: CN
Inventors: N��з��; N·托夫特; ж�; I·波斯托尔卡
Original assignee: Tetra Laval Holdings and Finance SA
Current assignee: Tetra Laval Holdings and Finance SA
Priority date: 1998-04-01
Filing date: 1999-03-30
Publication date: 2004-01-14
Anticipated expiration: 2019-03-30
Also published as: CN1304360A; RU2202473C2; WO1999050066A1; NO20004878L; ES2257857T3; JP2009035003A; EP1082220B1; BR9909348A; JP2002509820A; JP4193963B2; DE69930618D1; NO325830B1; AU739880B2; CN1495106A; CH693670A5; US6436547B1; JP4738459B2; NO20004878D0; NZ507470A; AR018831A1

Abstract

Translated fromChinese

一种层压包装材料(10)，它包括纸或纸板的芯层(11)和聚酰胺混合物的阻气层(12)，该聚酰胺混合物的阻气层包括间二甲苯二胺和已二酸(尼龙-MXD6)的缩聚物和第二结晶或半结晶聚酰胺，该缩聚物通过共挤涂布来涂敷在芯层(11)的一侧上。以及一种制造层压包装材料的方法和用层压包装材料制成的包装容器(30)。A laminated packaging material (10) comprising a core layer (11) of paper or paperboard and a gas barrier layer (12) of a polyamide blend comprising a polycondensate of m-xylenediamine and adipic acid (nylon-MXD6) and a second crystalline or semi-crystalline polyamide, the polycondensate being applied to one side of the core layer (11) by coextrusion coating. Also provided are a method for producing the laminated packaging material and a packaging container (30) made of the laminated packaging material.

Description

Translated fromChinese

一种层压包装材料，制造所述层压材料和由该层压材料制成的包装容器的方法A laminated packaging material, a method for manufacturing the laminated material and a packaging container made of the laminated material

技术领域technical field

本发明涉及一种层压包装材料，该层压包装材料包括纸或纸板的芯层和聚酰胺的阻气层，该聚酰胺的阻气层包括间二甲苯二胺和己二酸(尼龙-MXD6)的缩聚物，该缩聚物通过共挤涂布来涂敷在芯层以及至少一层热密封塑料层的一侧上。The present invention relates to a laminated packaging material comprising a core layer of paper or cardboard and a gas barrier layer of polyamide comprising m-xylylenediamine and adipic acid (Nylon-MXD6 ), which is applied by coextrusion coating on the core layer and on one side of at least one heat-sealable plastic layer.

本发明还涉及一种制造本发明的层压包装材料以及由该层压包装材料制成的包装容器的方法。The invention also relates to a method of manufacturing the laminated packaging material according to the invention and the packaging container made of the laminated packaging material.

背景技术Background technique

在包装工业中，公知的是采用专用性能的层压包装材料来包装和输送液体食物。通常，这种层压包装材料由刚性结构但可折叠的芯层组成，该芯层例如由纸或纸板制成，以获得良好的力学结构稳定性。塑料的液密涂层涂布在芯层的两侧，并有效的保护液体吸收纤维的芯层抵抗水分渗入。这些外层通常由热塑材料，最好是聚乙烯构成，聚乙烯还赋予包装材料极佳的热密封性能，因此，该包装材料可转化成具有理想的几何外形的成品包装物。In the packaging industry, it is known to use laminated packaging materials with special properties to package and deliver liquid foods. Typically, such laminated packaging materials consist of a rigid structural but foldable core layer, for example made of paper or cardboard, in order to obtain good mechanical structural stability. A liquid-tight coating of plastic is coated on both sides of the core and effectively protects the core of liquid-absorbent fibers against moisture penetration. These outer layers are usually constructed of a thermoplastic material, preferably polyethylene, which also imparts excellent heat-sealability to the packaging material, so that the packaging material can be converted into a finished package having the desired geometric shape.

层压包装材料仅由纸或纸板和液密塑料构成，然而面对气体，特别是氧气，它缺乏气密性。这是在包装许多食物中面临的最大缺点，食物接触氧气后，其保存期限，味道和营养含量急剧恶化。这种食物的一个例子是果汁，当果汁暴露在氧气中时，其维生素C含量降低。为了给包装材料提供阻气层，特别是阻挡氧气层，本领域中公知的是在芯层的打算转到面向成品包装物内部的一侧上涂布一层物质，该物质拥有极佳的氧气密封性能，例如铝箔(‘Alifoil’)，EVOH(乙烯乙烯醇)或PVOH(聚乙烯醇)。A laminated packaging material consists only of paper or cardboard and liquid-tight plastic, however it lacks airtightness against gases, especially oxygen. This is the biggest disadvantage faced in packaging many foods, when food is exposed to oxygen, its shelf life, taste and nutritional content deteriorate dramatically. An example of such a food is fruit juice, whose vitamin C content decreases when it is exposed to oxygen. In order to provide the packaging material with a gas barrier, especially an oxygen barrier, it is known in the art to coat the side of the core layer intended to face the interior of the finished package with a substance possessing excellent oxygen resistance. Sealing properties such as aluminum foil ('Alifoil'), EVOH (ethylene vinyl alcohol) or PVOH (polyvinyl alcohol).

通常理想的是能够制造在冷藏时具有所谓的“延长的保存期限”(ESL)的包装容器，即在8℃时储藏约6周后可保持维生素C含量和包装的产品的质量，在7℃时可储藏约8周，或者在4℃时可储藏约10周。It is generally desirable to be able to manufacture packaging containers that have a so-called "extended shelf life" (ESL) when refrigerated, i.e. maintain the vitamin C content and quality of the packaged product after storage at 8°C for about 6 weeks, and at 7°C Store for about 8 weeks at refrigerated water, or about 10 weeks at 4°C.

然而，公知的阻气层具有一些缺点，例如，从成本的观点来看，在一些情况下，在环境和回收方面，食物包装中代替铝箔作为阻气材料被认为是适合的。防渗聚合物例如EVOH和PVOH分别对潮气非常敏感，当它们暴露在潮湿环境下时，迅速的丧失了其抵抗氧气的阻气性能。其中，有必要用另一种聚合物层例如潮气不可渗入的聚乙烯层包绕阻气层EVOH和PVOH。或者，EVOH和PVOH分别可与一种或多种公知的食物认可的聚合物结合，以形成连续完好的整体层，该整体层具有在潮湿环境下也保留的极佳阻气性能。然而，制造分别包括EVOH和PVOH阻气层的包装材料需要的材料成本和用于制造必须的多层层压制品的成本高。这是因为在层压制品的每侧上，该阻气层必须由至少一个，通常两个塑料保护外层包绕。However, the known gas barrier layers have some disadvantages, for example from a cost point of view, and in some cases, environmental and recycling aspects, replacing aluminum foil as gas barrier material in food packaging is considered suitable. Barrier polymers such as EVOH and PVOH respectively are very sensitive to moisture and rapidly lose their gas barrier properties against oxygen when they are exposed to moisture. Here, it is necessary to surround the gas barrier layers EVOH and PVOH with another polymer layer, for example a moisture-impermeable polyethylene layer. Alternatively, EVOH and PVOH, respectively, can be combined with one or more well-known food-approved polymers to form a continuous, integral layer with excellent gas barrier properties that are also retained in wet environments. However, the material cost required to manufacture packaging materials including EVOH and PVOH gas barrier layers respectively and the cost for manufacturing the necessary multilayer laminate are high. This is because the gas barrier layer must be surrounded by at least one, usually two, protective outer layers of plastic on each side of the laminate.

美国专利477088公开了一种用于制造果汁包装的包装层压制品，该果汁包装由一个纸或纸板的芯层和涂布于其上的阻气层以及离聚物粘合剂层组成，该阻气层包括尼龙(没有详细描述)，该离聚物粘合剂层即涂布在阻气层上的Surlyn，以作为粘合到最内(朝向包装的内部)聚烯烃层上的中间粘合层。U.S. Patent 477088 discloses a packaging laminate for the manufacture of fruit juice packaging consisting of a core layer of paper or cardboard and coated thereon with a gas barrier layer and an ionomer adhesive layer, the The gas barrier layer comprises nylon (not described in detail), and the ionomeric adhesive layer, Surlyn®, is coated on the gas barrier layer as an intermediate bonded to the innermost (towards the inside of the package) polyolefin layer. adhesive layer.

EP0520767公开了一种由纸或纸板的芯层、阻气层和涂布于其间的粘合层构成的包装层压制品，该阻气层包括非晶态聚酰胺(Selar PA3426美国杜邦公司)。EP0520767 discloses a packaging laminate consisting of a core layer of paper or cardboard, a gas barrier layer and an adhesive layer coated therebetween, the gas barrier layer comprising amorphous polyamide (Selar PA3426 DuPont, USA).

然而，这些公知的包装层压制品的主要缺点是它们不具有足够好的阻气性能，因而不能以经济的聚合物层厚度来延长包装的保存期限。However, a major disadvantage of these known packaging laminates is that they do not have sufficiently good gas barrier properties to prolong the shelf life of the packaging with economical polymer layer thicknesses.

具有名为“尼龙-MXD6”的间二甲苯二胺和己二酸的聚酰胺缩聚物是半结晶聚酰胺，并且与其它传统的聚酰胺相比具有特殊的性能，例如高的抗张强度和抗挠强度和模量，较高的玻璃态转化温度，较低的吸水率，以及极佳的阻挡例如氧气的阻气性。The polyamide condensation polymer of m-xylylenediamine and adipic acid named "Nylon-MXD6" is a semi-crystalline polyamide and has special properties compared to other conventional polyamides, such as high tensile strength and resistance Flexural strength and modulus, high glass transition temperature, low water absorption, and excellent gas barrier properties such as oxygen.

美国专利5164267(已放弃)描述了一种层压复合物，该层压复合物由基于纤维素材料的衬底层与多层膜层压构成，该多层膜包括至少一层基于聚酰胺的层，该聚酰胺由脂肪族二羧酸与二甲苯二胺缩聚制成，例如尼龙-MXD6，其中多层膜共挤涂布在衬底上，且聚烯烃层是与衬底接触的接触层。US Patent 5164267 (abandoned) describes a laminated composite consisting of a substrate layer based on cellulose material laminated with a multilayer film comprising at least one layer based on polyamide , the polyamide is made by polycondensation of aliphatic dicarboxylic acid and xylenediamine, such as nylon-MXD6, where the multilayer film is coextrusion coated on the substrate, and the polyolefin layer is the contact layer in contact with the substrate.

然而，实际上不可能将仅由尼龙-MXD6构成的阻气层用于液体食物纸板或纸板箱包装层压制品中，因为，例如在形成和折叠包装材料时，该材料提供很容易破裂的易碎层，因此对气体和液体的阻挡效果很差。而且，在消极的将包装材料密封到包装容器内的过程中，该过程还导致包装具有较差的气封，此时，在阻气层内的尼龙-MXD6也似乎影响热封性能。However, it is practically impossible to use a gas barrier layer consisting only of Nylon-MXD6 in liquid food cardboard or carton packaging laminates because, for example, when forming and folding the packaging material, the material provides a Fractal and therefore a poor barrier to gases and liquids. Also, in the process of negatively sealing the packaging material into the packaging container, which also resulted in a package with a poor air seal, Nylon-MXD6 in the gas barrier layer also appeared to affect heat seal performance at this time.

JP-A-06305086描述了二轴向张紧的聚酰胺膜和纸层的层压制品，其中聚酰胺膜包括至少两个聚酰胺层，至少其中一个层包含尼龙-MXD6。通过干燥层压法，利用粘合剂，或通过挤压层压法，双轴取向膜层压到纸层上。这样，通过不同的工艺，例如吹膜法，预制该双轴膜，然后层压到其它层上。JP-A-06305086 describes a laminate of biaxially tensioned polyamide film and paper layers, wherein the polyamide film comprises at least two polyamide layers, at least one of which comprises nylon-MXD6. The biaxially oriented film is laminated to the paper layer by dry lamination, with an adhesive, or by extrusion lamination. Thus, the biaxial film is prefabricated by different processes, such as blown film, and then laminated to other layers.

JP-A-06305086中产生的层压制品与本发明的权利要求1的层压制品差别很大。为了在纸层和聚酰胺层之间提供粘合，必须采用粘合剂，例如尿脘粘合剂、丙烯酸粘合剂和聚酯粘合剂，或者中间粘合层，在层压制品中它们依次需要多种和/或不同的材料，这样，从工作环境和自然资源管理的角度来看，导致产生较高的成本和较高的环境破坏。而且，在这种层压制品中，在纸层和聚酰胺层之间的粘合最可能是最差，因为预制膜的表面氧化和/或硬化，而且不能很容易地粘合到挤压粘合层上。特别是，制造这种层压制品的工艺更繁琐，而且成本效率很低，因为它需要预制双轴取向膜的附加步骤。The laminate produced in JP-A-06305086 is very different from that ofclaim 1 of the present invention. To provide adhesion between the paper and polyamide layers, adhesives such as urethane, acrylic, and polyester must be used, or an intermediate adhesive layer, which in laminates This in turn requires multiple and/or different materials, which leads to higher costs and higher environmental damage from the point of view of the working environment and natural resource management. Also, in such laminates, the adhesion between the paper layer and the polyamide layer is most likely to be the worst, since the surface of the preformed film oxidizes and/or hardens, and cannot easily bond to the extrusion bond. combined layer. In particular, the process for making such laminates is more cumbersome and very cost-ineffective because it requires the additional step of prefabricating the biaxially oriented film.

发明概要Summary of the invention

因此，本发明的一个目的是提供一种所述类型的新颖的、节省成本、环境良好和良好整体性的层压包装材料，它具有极佳的阻气性，特别是阻挡氧气，以及良好的阻液性，和良好的力学性能，例如在层之间的弹性和粘合强度。It is therefore an object of the present invention to provide a novel, cost-effective, environmentally benign and good-integrity laminated packaging material of the type described, which has excellent gas barrier properties, in particular oxygen, and good Liquid resistance, and good mechanical properties such as elasticity and adhesive strength between layers.

本发明的另一个目的是提供一种用于制造包装容器的包装材料，该包装容器特别适合储藏果汁，它具有在冷藏条件下约6-10周的延长的保存期限。Another object of the present invention is to provide a packaging material for the manufacture of a packaging container particularly suitable for storing fruit juices, which has an extended shelf life of about 6-10 weeks under refrigerated conditions.

根据本发明通过一种层压的包装材料可获得这些目的，该层压包装材料包括纸或纸板的芯层和聚酰胺的阻气层，该聚酰胺的阻气层包括间二甲苯二胺和己二酸(尼龙-MXD6)的缩聚物，该缩聚物通过共挤涂布来涂敷在芯层以及至少一层热封塑料层的一侧上，其中阻气层还包括一个第二结晶聚酰胺或半结晶聚酰胺。These objects are achieved according to the invention by a laminated packaging material comprising a core layer of paper or cardboard and a gas barrier layer of polyamide comprising m-xylylenediamine and hexylene Polycondensate of diacid (Nylon-MXD6) applied by coextrusion coating on the core layer and on one side of at least one heat-sealable plastic layer, wherein the gas barrier layer also comprises a second crystalline polyamide or semi-crystalline polyamide.

通过将尼龙-MXD6与另一种结晶或半结晶聚酰胺混合，例如PA-6或PA-6/66，其性能可自行设计，因此可获得例如在破裂处改进的伸长率和改进的密封性。在尼龙-MXD6的破裂处的伸长率仅约为2.3％。对于标准的PA-6，它通常是400-600％。然而，过高含量的PA-6将导致较差的阻气性，因为这按指数规律随PA-6的含量而降低。在该文中，可使用的聚酰胺的例子是聚酰胺-6(PA-6)、PA-66、PA-6/66及其混合物。By mixing Nylon-MXD6 with another crystalline or semi-crystalline polyamide, such as PA-6 or PA-6/66, its properties can be tailored, thus obtaining e.g. improved elongation at ruptures and improved sealing sex. The elongation at break of nylon-MXD6 is only about 2.3%. For standard PA-6 it is usually 400-600%. However, too high a content of PA-6 will lead to poor gas barrier properties, since this decreases exponentially with the content of PA-6. Examples of usable polyamides in this context are polyamide-6 (PA-6), PA-66, PA-6/66 and mixtures thereof.

最好，根据本发明，尼龙-MXD6和第二结晶聚酰胺的混合物是不混溶混合物，即两相混合物。对其的DSC测量表示两个不同的熔点或间隔，即它表示两个而不是一个熔化峰值，尼龙-MXD6作为基体，这种不混溶混合物具有进一步改进阻氧性能以及改进的抗张强度的优点。Preferably, according to the invention, the mixture of nylon-MXD6 and the second crystalline polyamide is an immiscible mixture, ie a two-phase mixture. The DSC measurement on it shows two different melting points or intervals, i.e. it shows two melting peaks instead of one, Nylon-MXD6 as matrix, this immiscible mixture has further improved oxygen barrier properties as well as improved tensile strength advantage.

为了获得在阻气性、力学性能、密封强度和抵抗鼓胀方面最佳的性能，根据本发明在阻气层中的混合物中包含的尼龙-MXD6的比例以重量百分比计大于50％并小于100％，较好的是60％到90％，更好的是70％到80％。In order to obtain the best properties in terms of gas barrier properties, mechanical properties, sealing strength and resistance to bulging, the proportion of nylon-MXD6 contained in the mixture in the gas barrier layer according to the invention is greater than 50% and less than 100% by weight , preferably 60% to 90%, more preferably 70% to 80%.

根据本发明的一个优选实施例，第二聚酰胺是“尼龙粘土混合物”(NCH)，这是由结晶聚酰胺，例如PA-6、PA-66、PA-6/66或PA-12，以及均匀分布的硅酸盐层构成的分子合成物。通过将粘土矿物分散在单体中并使之聚合，这样，NCH在聚合工艺中形成，从而在尼龙聚合物中产生了极细和良好分散的硅酸盐片晶形态。这样，导致改进的阻氧性能和极佳的力学性能。在“应用聚合物科学杂志第49卷，1259-1264(1993)”，和“第55卷119-123(1995)”中描述了这种聚酰胺。PA-6的优点是成本低，而基于PA-6，PA-66或PA-6/66的NCH的优点在于与其各基础聚合物相比，它具有明显较好的阻氧气性能，而且NCH比纯PA-6的阻挡潮气性能好，约是其两倍。适合本发明的混合物的NCH的一个例子是基于PA-6，并且可从UBE工业公司商业上获得(1022CM1等级)。According to a preferred embodiment of the present invention, the second polyamide is "nylon clay mixture" (NCH), which is made of crystalline polyamide, such as PA-6, PA-66, PA-6/66 or PA-12, and Molecular composition of uniformly distributed silicate layers. By dispersing the clay mineral in the monomer and polymerizing it, NCH is formed during the polymerization process, resulting in an extremely fine and well-dispersed silicate platelet morphology in the nylon polymer. This results in improved oxygen barrier properties and excellent mechanical properties. Such polyamides are described in "Journal of Applied Polymer Science Vol. 49, 1259-1264 (1993)", and "Vol. 55, 119-123 (1995)". The advantage of PA-6 is low cost, and the advantage of NCH based on PA-6, PA-66 or PA-6/66 is that it has significantly better oxygen barrier performance compared with its respective base polymers, and NCH is more The moisture barrier performance of pure PA-6 is about twice as good. An example of an NCH suitable for a mixture of the invention is based on PA-6 and is commercially available from UBE Industries (1022CM1 grade).

通过这样使尼龙-MXD6与基于例如PA-6的NCH混合，可获得最优的阻气性能以及机械性能。尼龙-MXD6的比例(其成本相对较高)可降低，且其阻气性不会损失到与采用纯PA-6相同的程度。与此同时，还获得一种混合物，它具有在破裂处显著较高的伸长率，因此在成形和折叠时对破裂成形具有较大的阻力，以提供均匀的气密阻挡层。以重量百分比计，75％的尼龙-MXD6和25％的NCH-PA6的混合物在破裂处具有超过200％的伸长率。By mixing nylon-MXD6 in this way with NCH based eg on PA-6, optimum gas barrier properties as well as mechanical properties can be obtained. The proportion of nylon-MXD6 (which is relatively expensive) can be reduced without losing its gas barrier properties to the same extent as with pure PA-6. At the same time, a mixture is obtained which has a significantly higher elongation at rupture and thus a greater resistance to rupture formation during forming and folding to provide a uniform airtight barrier. A blend of 75% Nylon-MXD6 and 25% NCH-PA6 has an elongation at break of over 200% in weight percent.

而且，通过采用作为尼龙-MXD6混合物的第二成分的NCH，降低了“鼓胀”效应。“鼓胀”意味着包装容器壁从包装的角部之间的垂直平面向外膨胀的效果。利用NCH对鼓胀增加的阻力很可能是部分由于NCH材料本身的刚度性能的作用。NCH-PA6的抗张模量例如约为830-880，而对于PA-6它仅是约580-600N/mm²。另外，NCH的潮阻气挡性能好的程度接近PA-6的两倍。重要的是降低鼓胀效应，因为在一些国家的顾客对包装容器的鼓胀外观特别有偏见，他们相信鼓胀外观意味着食物产品已经发酵。Also, by using NCH as the second component of the nylon-MXD6 blend, the "bulging" effect is reduced. "Bulking" means the effect of the walls of the packaging container expanding outward from a vertical plane between the corners of the packaging. The increased resistance to inflation with NCH is likely due in part to the inherent stiffness properties of the NCH material. The tensile modulus of NCH-PA6 is eg about 830-880, whereas for PA-6 it is only about 580-600 N/mm² . In addition, the moisture barrier performance of NCH is nearly twice that of PA-6. It is important to reduce the puffing effect because consumers in some countries are particularly prejudiced against the puffy appearance of packaging containers, believing that the puffy appearance means that the food product has fermented.

根据本发明的第二优选实施例，提供更加节省成本和环境良好的包装层压制品，其中进一步改进了阻气性能，与此同时，提供适合制造具有改进密封性的包装容器的包装层压制品。通过直接在纸或纸板的芯层上共挤涂布，而不需要任何中间粘合剂或粘合聚合物层，这样，涂敷聚酰胺阻气层，从而实现上述目的。以这种方式，中间粘合层多余，这样节省了材料，从环境资源回收和成本的观点来看，这样提供了更经济的层压制品。这样，术语“挤压涂布”意味着在衬底上同时挤压和涂布一层可挤压塑料，这与所谓的“挤压层压”不同，该挤压层压是通过在衬底层的网和预制膜层之间挤压中间粘合层，以便将预制膜层压到衬底上。已经显示出具有三层结构，即尼龙-MXD6混合阻气层，复合薄膜粘结层和通过共挤涂布在芯层的内侧上的聚烯烃层，的层压制品的阻气性与具有5层结构的层压制品相比提高约30-40％，该5层制品还具有与纸板层接触的聚烯烃层，和在聚烯烃层与阻气层之间的复合薄膜粘结层。According to a second preferred embodiment of the present invention, a more cost-effective and environmentally friendly packaging laminate is provided, wherein the gas barrier properties are further improved, and at the same time, a packaging laminate suitable for manufacturing packaging containers with improved airtightness is provided . This is achieved by applying the polyamide gas barrier layer directly on the core layer of the paper or board without any intermediate adhesive or binding polymer layer by coextrusion coating. In this way, the intermediate bonding layer is redundant, which saves material and thus provides a more economical laminate from an environmental resource recovery and cost standpoint. Thus, the term "extrusion coating" means simultaneously extruding and coating a layer of extrudable plastic on a substrate, as opposed to so-called "extrusion lamination", which The intermediate adhesive layer is squeezed between the web and the prefabricated film layer to laminate the prefabricated film to the substrate. It has been shown that the gas barrier properties of laminates with a three-layer structure, namely a nylon-MXD6 hybrid gas barrier layer, a composite film tie layer and a polyolefin layer coated on the inner side of the core layer by co-extrusion, are comparable to those with 5 About 30-40% improvement compared to the laminate of the ply structure, the 5 ply product also has a polyolefin layer in contact with the paperboard layer, and a composite film tie layer between the polyolefin layer and the gas barrier layer.

而且，在第一步骤中，当共挤纸板上的三层结构时，与当共挤纸板上的具有两个外聚烯烃层的5层结构相比，三层的最外聚烯烃层可在较低温度下挤压。通常是这种情况(最好在一个工艺中包含尽可能少的挤压机)，即在通过三个挤压机和一个5层进给机进行5层共挤时，两个外层必须在相同温度下挤压。为了在LDPE层和纸板之间提供粘合剂，约320℃的温度是理想的。然而，对于层压制品的外层，LDPE可在280℃的更低温度下挤压。在该低温下挤压的LDPE承受很少的氧化并将非常适合在将包装层压制品转化成纸容器的过程中进行随后的热封。如果在低温下挤压聚乙烯，则消除了产生包装产品的“塑料味道”的危险。在5层结构中，其中间的一些地方的挤压温度必须选择折衷，以便平衡粘合到纸板上，以抵抗外LDPE层的热封性，因为两个LDPE层由相同的挤压机挤压。Also, in the first step, when co-extruding a three-layer structure on paperboard, the outermost polyolefin layer of the three-layer can be Extrude at a lower temperature. This is often the case (preferably with as few extruders as possible in a process) that in a 5-layer coextrusion through three extruders and a 5-layer feeder, the two outer layers must be in Extrude at the same temperature. To provide an adhesive between the LDPE layer and the paperboard, a temperature of about 320°C is ideal. However, for the outer layer of the laminate, LDPE can be extruded at a lower temperature of 280°C. LDPE extruded at this low temperature suffers little oxidation and will be well suited for subsequent heat sealing during conversion of packaging laminates into paper containers. If the polyethylene is extruded at low temperature, the danger of developing a "plastic taste" of the packaged product is eliminated. In a 5-layer structure, the extrusion temperature somewhere in the middle has to be chosen as a compromise in order to balance the bonding to the paperboard against the heat-sealability of the outer LDPE layer, since both LDPE layers are extruded by the same extruder .

包括尼龙-MXD6和PA-6或NCH的混合物的阻气层证实非常良好的粘合到纸或纸板的芯层上，该粘合以制造节省成本的层压制品所必须的高线速度进行。这根本不是自信，因为在该方面不同的聚酰胺具有不同的性能。PA-6通常良好的粘合到纸板上，与此同时，非晶态聚酰胺不能粘合。具有良好的粘合意味着塑料层粘合到纸板上，同时其强度大于纸板本身内的内聚性。这样，在剥离试验中破坏的外观发生在纸板层内，而不是在层之间。这可以看到，“剥离的”塑料层表面由纸纤维覆盖，类似的，PA-6和NCH的混合物层或NCH层没有粘合到纸板上，而尼龙-MXD6一定程度上粘合。然而，在尼龙-MXD6和纸之间的粘合很容易破坏，因为尼龙-MXD6层易碎，而且本身不可弯曲，当层压制品弯曲或扭曲时将破裂并与纸板分层。A gas barrier layer comprising a blend of nylon-MXD6 and PA-6 or NCH demonstrates very good adhesion to the core layer of paper or paperboard at the high line speeds necessary for the manufacture of cost-effective laminates. This is not at all confident, since different polyamides have different properties in this respect. PA-6 generally bonds well to paperboard, while amorphous polyamides do not. Having good adhesion means that the plastic layer is bonded to the cardboard while being stronger than the cohesion within the cardboard itself. This way, the appearance of failure in the peel test occurs within the paperboard plies rather than between plies. It can be seen that the surface of the "peeled" plastic layer is covered by paper fibers, similarly the layer of mixture of PA-6 and NCH or the layer of NCH is not bonded to the paperboard, while the nylon-MXD6 is bonded to some extent. However, the bond between nylon-MXD6 and paper is easily broken because the nylon-MXD6 layer is brittle and inflexible by itself and will crack and delaminate from the paperboard when the laminate is bent or twisted.

与具有聚乙烯中间层的芯层上的阻气层的层压制品相比，还证实了阻气层直接设在芯层上导致接近30-40％的改进的阻挡氧气性。这可能是因为在芯层和直接设置的阻气层之间潮气相等。当阻气层直接与纸或纸板层接触时，即结果是渗进阻气层内的包装容器的内含物的潮气分布到芯层和阻气层上，结果较小比例的潮气留在聚酰胺层内，因此，在这种特别情况下，阻气层内保持较好的阻气性。It has also been demonstrated that the direct placement of the gas barrier layer on the core layer results in an improved oxygen barrier of approximately 30-40%, compared to laminates with a gas barrier layer on a core layer of polyethylene interlayer. This may be due to the equalization of moisture between the core layer and the directly disposed gas barrier layer. When the gas barrier layer is in direct contact with the paper or cardboard layer, that is, the result is that the moisture of the contents of the packaging container penetrated into the gas barrier layer is distributed to the core layer and the gas barrier layer, with the result that a smaller proportion of the moisture remains in the polystyrene layer. In the amide layer, therefore, in this particular case, better gas barrier properties are maintained in the gas barrier layer.

阻氧性能的令人吃惊的增加通常不发生所有聚酰胺上，特别是仅发生在尼龙-MXD6，很可能是因为尼龙-MXD6的阻气性在较高的湿度下降低，在液体食物产品包装情况下通常如此。The surprising increase in oxygen barrier properties generally does not occur for all polyamides, especially only for nylon-MXD6, most likely because the gas barrier properties of nylon-MXD6 decrease at higher humidity, and in liquid food product packaging This is usually the case.

阻气层实际上可使用任何理想的厚度，但根据本发明的一个优选实施例，它特别适合用于果汁的包装容器中，该包装容器具有延长的保存期限，阻气层用在接近3-30克/米²，较好的是4-12克/米²，最好的是5-8克/米²的芯层上。其原因是在低于5克/米²的用量下，应用进程的不确定性和阻挡性可能较大。在应用数量大于8克/米²时，包装层压制品的成本节约很少。The gas barrier layer can be used in virtually any desired thickness, but according to a preferred embodiment of the present invention, it is particularly suitable for use in fruit juice packaging containers, the packaging container has an extended shelf life, and the gas barrier layer is used in close to 3- 30 g/m² , preferably 4-12 g/m² , most preferably 5-8 g/m² on the core layer. The reason is that at dosages below 5 g/m² , the application process may be more uncertain and obstructive. At application quantities greater than 8 g/^m2 , the cost savings of packaging laminates are minimal.

在转向面朝离开芯层的阻气层的一侧，可涂布聚烯烃层，该聚烯烃层通过涂布在阻气层和聚烯烃层之间的粘合聚合物层粘合到阻气层上。聚烯烃层可包括不同类型的聚乙烯，例如超低密度聚乙烯(ULDPE)，低密度聚乙烯(LDPE)，线性低密度聚乙烯(LLDPE)和茂合金属聚乙烯(m-PE)或其混合物。特别是，m-PE和m-PE与一些上述公开类型的聚乙烯的混合物使包装材料在热密封时具有极紧的密封性，以形成完成的包装容器，这还有助于包装容器的气密性。这样，包装容器的气封性取决于包装材料本身的气封性和密封如何紧固，这有可能由包装材料制造包装容器。On the side turned towards the gas barrier layer away from the core layer, a polyolefin layer can be coated, which is bonded to the gas barrier layer by an adhesive polymer layer coated between the gas barrier layer and the polyolefin layer. layer. The polyolefin layer may comprise different types of polyethylene such as ultra low density polyethylene (ULDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and metallocene polyethylene (m-PE) or mixture. In particular, m-PE and blends of m-PE with some of the above-disclosed types of polyethylene provide the packaging material with an extremely tight seal when heat-sealed to form the finished packaging container, which also contributes to the airtightness of the packaging container. Tightness. In this way, the airtightness of the packaging container depends on the airtightness of the packaging material itself and how fast the seal is, and it is possible to manufacture the packaging container from the packaging material.

布置在阻气层和聚烯烃层之间的粘合聚合物层例如由用羧酸原子团改性的聚乙烯构成，该聚乙烯例如是用顺丁烯二酸酐接枝的聚乙烯，例如一些种类的Admer和Bynel。或者，可使用粘合聚合物与PE的混合物，以提供粘合到聚酰胺阻气层。The adhesive polymer layer arranged between the gas barrier layer and the polyolefin layer consists, for example, of polyethylene modified with carboxylic acid radicals, such as polyethylene grafted with maleic anhydride, such as some species Admer(R) and Bynel(R). Alternatively, a blend of adhesive polymers and PE may be used to provide adhesion to the polyamide gas barrier layer.

两个外聚烯烃层的目的是，一方面保护包装材料不被潮气和液体从外部渗入，另一方面，通过传统的所谓热密封来使包装材料具有可密封的主要功能，因此，在提供热和压力下，塑料的相互面对层可通过表面熔化连接在一起。在包装材料转化成包装容器期间，热密封形成力学性能较强的液体密封接头。为了提供具有良好紧密性的密封，内聚烯烃层涂布成接近15-35克/米²，较好的是25-30克/米²，且外聚烯烃层的数量接近12-20克/米²，较好的是15-20克/米²。在LDPE在内层的情况下，该数量应至少接近25克/米²，最好接近30克/米²。内聚烯烃层13还可以用作两个或多个分离的聚烯烃层，该聚烯烃层由相同的或不同类型的聚烯烃构成，其数量加起来为上述数量。The purpose of the two outer polyolefin layers is, on the one hand, to protect the packaging material from the infiltration of moisture and liquids from the outside, and, on the other hand, to give the packaging material its main function of being sealable by conventional so-called heat sealing, thus providing heat and under pressure, mutually facing layers of plastic can be bonded together by surface melting. During the conversion of the packaging material into a packaging container, heat sealing creates a mechanically strong, liquid-tight joint. In order to provide a seal with good tightness, the inner polyolefin layer is coated in an amount close to 15-35 g/m² , preferably 25-30 g/m² , and the amount of the outer polyolefin layer is close to 12-20 g/m 2 .^m2 , preferably 15-20 g/^m2 . In the case of an LDPE inner layer, this amount should be at least approximately 25 g/^m2 , preferably approximately 30 g/^m2 . The inner polyolefin layer 13 can also be used as two or more separate polyolefin layers consisting of the same or different types of polyolefins, the numbers of which add up to the above-mentioned number.

外聚烯烃层可设有适当的装饰印刷和/或识别包装产品的信息性质，该外聚烯烃层涂布在芯层侧面上的包装材料上，并在完成的包装容器内打算转到面向外部。The outer polyolefin layer may be provided with suitable decorative printing and/or informational properties identifying the packaged product, which outer polyolefin layer is coated on the packaging material on the side of the core layer and is intended to be turned to face outward in the finished packaging container .

根据本发明的第三优选实施例，在转化成包装容器的工艺中，提供具有改进的密封性的包装层压制品。已经发现重要的是，层压制品的两个外热塑层的一些最小厚度/表面重量，用以获得最优强度，气密密封和降低的鼓胀。对于具有三层共挤涂布的阻挡膜的层压制品来说，这是很明显的。在这种三层层压制品中，包含极少的阻液塑料，且鼓胀的危险增加。可以看到，为了增加密封强度和降低鼓胀，在最内层的密封聚合物的量，即在包装层压制品的内侧上，最好低密度聚乙烯(LDPE)应至少为25克/米²。当聚酰胺阻挡层和复合薄膜粘结层分别以数量为约6和约3克/米²来涂敷，而LDPE的最外层最好应具有约15-20克/米²的表面重量，换句话说，在纸板的内部上的阻液聚合物的总量和在纸板外部的聚合物的量之间应有一定关系。由于液体和气体的密封接头的密封强度和刚度改进，包装容器在其包装产品中的维生素C的剩余量得以改进。很少的潮气通过密封渗入层压制品本身，这导致对容器壁的鼓胀的改进的阻力。因此，通过调节外聚烯烃层的量，因此在最内层的LDPE量至少为25克/米²，最好是30克/米²，且外层的量小于20克/米²，最好是约16克/米²，阻挡层涂布成5-8克/米²，复合薄膜粘结层涂布成3-6克/米²，这些改进的性能得到固定。从5层层压制品也可看到这种效果。然而，其数量比三层层压制品的限制少。然而，最惊奇的是，与对应的5层层压制品相比，三层层压制品具有改进的密封强度和鼓胀特性，5层层压制品中，更大量的阻挡液体聚烯烃涂敷在朝向产品的芯层的内侧。According to a third preferred embodiment of the present invention, a packaging laminate is provided with improved hermeticity during conversion into a packaging container. It has been found important that some minimum thickness/surface weight of the two outer thermoplastic layers of the laminate be obtained for optimal strength, hermetic sealing and reduced bulging. This is evident for laminates with a three-layer coextrusion coated barrier film. In such three-layer laminates, very little liquid-resistant plastic is included and the risk of bulging is increased. It can be seen that in order to increase seal strength and reduce bulging, the amount of seal polymer in the innermost layer, i.e. on the inner side of the packaging laminate, preferably low density polyethylene (LDPE) should be at least 25 g/^m2 . When the polyamide barrier layer and the composite film tie layer are applied in amounts of about 6 and about 3 g/m² respectively, the outermost layer of LDPE should preferably have a surface weight of about 15-20 g/m² , for In other words, there should be a relationship between the total amount of liquid blocking polymer on the inside of the paperboard and the amount of polymer on the outside of the paperboard. Due to the improved seal strength and rigidity of the sealed joints of liquid and gas, the residual amount of vitamin C of the packaging container in its packaged product is improved. Less moisture penetrates through the seal into the laminate itself, which results in improved resistance to bulging of the container walls. Therefore, by adjusting the amount of the outer polyolefin layer, the amount of LDPE in the innermost layer is at least 25 g/^m2 , preferably 30 g/^m2 , and the amount of the outer layer is less than 20 g/^m2 , preferably It is about 16 g/^m2 , the barrier layer is coated at 5-8 g/^m2 , and the composite film tie layer is coated at 3-6 g/^m2 , and these improved properties are fixed. This effect can also be seen from 5-layer laminates. However, its quantity is less restrictive than a three-layer laminate. Most surprisingly, however, the three-layer laminate had improved seal strength and swelling characteristics compared to the corresponding 5-layer laminate in which a greater amount of barrier liquid polyolefin was applied towards The inner side of the core layer of the product.

根据本发明的第四优选实施例，提供节省成本的包装层压制品，它具有进一步延长的保存期限，以及良好的芳香和味道保留性能，所谓的不会刮光表层的性能。According to a fourth preferred embodiment of the present invention, a cost-effective packaging laminate is provided, which has a further extended shelf life, and good aroma and taste retention properties, so-called non-scratch properties.

尼龙-MXD6材料本身还具有极佳的“阻挡芳香”性能，即朝向阻挡芳香和味道物质的阻挡性能，所谓的不会刮光表层的性能。The nylon-MXD6 material itself also has excellent "aroma blocking" performance, that is, the barrier performance towards blocking fragrance and taste substances, so-called performance that will not scratch the surface layer.

优选的层压制品的阻气性和在层压制品的包装产品内的维生素C的保留量进一步改善。通过包装层压制品获得这些目的，该包装层压制品具有沉积在纸板衬底芯层内侧上的第一阻挡层和第二阻挡层，该第二阻挡层包括尼龙-MXD6和第二结晶或半结晶聚酰胺的混合物，并进一步朝向内部和包装产品沉积，在最内部的阻挡层和包装产品之间具有较薄的复合薄膜粘结层和聚乙烯产品接触层。由于少量的聚烯烃聚合物用作层压制品的最内层，可防止非极性物质例如某些味道和芳香物质刮光以便从产品进入包装材料内。芳香和味道物质移动进入较薄的产品接触层内，但当它们到达尼龙-MXD6和第二结晶或半结晶聚酰胺的混合物的阻挡层时，可防止它们进一步移动，因此很少的所述物质能够吸收进入聚烯烃层。在该优选的包装层压制品中，由于最内部的聚乙烯层较薄，当将层压制品转化和密封成包装容器时，它不足以产生密封粘合。因此，热塑聚合物的另外密封层用于芯层的内侧，在最内阻挡层的另一侧上，即在第一和第二阻挡层之间。在密封时，相当薄的产品接触层和最内的阻挡层将“密封”，即在这些层中的聚合物将熔化，并且热量将到达而且熔化可热密封聚合物的中间层。以这种方式，尽管层压制品的外层内侧较薄，将可获得更多的热密封聚合物以产生热密封。The gas barrier of the preferred laminate and the retention of vitamin C within the packaged product of the laminate are further improved. These objects are achieved by a packaging laminate having a first barrier layer deposited on the inside of a paperboard substrate core and a second barrier layer comprising nylon-MXD6 and a second crystalline or semi- A blend of crystalline polyamides and further deposited towards the interior and packaging product with a thinner laminated film tie layer and polyethylene product contact layer between the innermost barrier layer and packaging product. Since a small amount of polyolefin polymer is used as the innermost layer of the laminate, non-polar substances such as certain flavor and aroma substances can be prevented from scratching off from the product into the packaging material. Fragrance and taste substances migrate into the thinner product contact layer, but when they reach the barrier layer of the blend of nylon-MXD6 and a second crystalline or semi-crystalline polyamide, they are prevented from moving further, so very little of said substances Capable of absorbing into the polyolefin layer. In this preferred packaging laminate, since the innermost polyethylene layer is relatively thin, it is insufficient to create a hermetic bond when the laminate is converted and sealed into a packaging container. Therefore, an additional sealing layer of thermoplastic polymer is used inside the core layer, on the other side of the innermost barrier layer, ie between the first and second barrier layer. When sealing, the relatively thin product contact layer and the innermost barrier layer will "seal", ie the polymer in these layers will melt and heat will reach and melt the intermediate layer of heat sealable polymer. In this way, despite the thinner inner side of the outer layer of the laminate, more heat seal polymer will be available to create the heat seal.

该优选的高性能ESL包装层压制品当然还具有与纸板直接接触的阻气层的优点，由于在阻气层内较低的潮气含量，提供30-40％的改进的阻气性。The preferred high performance ESL packaging laminates of course also have the advantage of a gas barrier layer in direct contact with the paperboard, providing 30-40% improved gas barrier properties due to lower moisture content in the gas barrier layer.

根据本发明的另一方面，提供本发明的包装层压制品的制造方法。According to another aspect of the present invention there is provided a method of manufacturing the packaging laminate of the present invention.

本发明的层压包装材料最好通过单步共挤出工艺制造，其中在芯层内部上的所有聚合物层通过共挤作用在芯层。在所述单步共挤工艺之前或之后，可热密封聚合物可涂敷到芯层外侧上，即芯层侧面转到面朝离开阻挡层。共挤的一个重要的优点是熔融聚合物的热量在多层挤压膜中良好的保存，直到挤压膜冲击衬底，在该衬底上挤压涂敷，这样，提供改进的粘合到衬底上(由于所谓的热惯性)。另一个优点是节省了另外的挤压处理步骤，这样提供更多时间和节省成本的工艺。The laminated packaging material of the present invention is preferably produced by a single-stage coextrusion process wherein all polymer layers on the inside of the core layer are coextruded onto the core layer. Before or after the single-step coextrusion process, the heat sealable polymer can be applied on the outside of the core layer, ie the core layer is turned sideways to face away from the barrier layer. An important advantage of coextrusion is that the heat of the molten polymer is well preserved in the multilayer extruded film until the extruded film impacts the substrate on which the extrusion coats, thus providing improved adhesion to on the substrate (due to the so-called thermal inertia). Another advantage is that an additional extrusion processing step is saved, which provides a more time and cost-effective process.

为了在多层共挤膜和纸板衬底之间获得足够的粘合，表面应通过预处理例如电晕处理和/或火焰处理或臭氧处理来激活，这种表面激活处理方法在本领域是公知的。最好，纸板衬底通过火焰处理和/或电晕处理来预处理，其中火焰处理是最佳的，而新挤压膜最好在它涂敷到纸板上之前用臭氧处理。In order to obtain adequate adhesion between multilayer coextruded films and paperboard substrates, the surface should be activated by pretreatments such as corona treatment and/or flame treatment or ozone treatment, such surface activation treatments are well known in the art of. Preferably, the paperboard substrate is pretreated by flame treatment and/or corona treatment, with flame treatment being most preferred, while the freshly extruded film is preferably treated with ozone before it is applied to the paperboard.

根据本发明由层压包装材料制成的结构稳定的包装容器可设有打开装置，这种开/关装置对于在液体食物包装领域中的普通技术人员是公知的。The structurally stable packaging container made of laminated packaging material according to the invention can be provided with opening means, such opening/closing means are well known to those skilled in the art of liquid food packaging.

由于本发明，提供一种环境更友善的，节约成本和制造经济的包装材料，它具有极佳的阻气性，特别是阻挡氧气性，即使在暴露到潮湿环境下也是如此。根据本发明的包装材料还具有良好的内聚性，以便使用用于制造适合液体食物特别是果汁的包装容器时抵抗分层，该包装材料可以所谓延长保存期限，即在冷藏条件下保存至多4-12周的时间。Thanks to the present invention, a more environmentally friendly, cost-effective and economical to manufacture packaging material is provided, which has excellent gas barrier properties, especially oxygen barrier properties, even when exposed to moisture. The packaging material according to the invention also has good cohesive properties in order to resist delamination when used for the manufacture of packaging containers suitable for liquid food, especially fruit juices, which can be so-called extended shelf life, i.e. stored under refrigerated conditions for up to 4 -12 week period.

附图的简要描述Brief description of the drawings

下面参见附图并根据实施例来详细描述本发明，其中：The present invention is described in detail below with reference to accompanying drawing and according to embodiment, wherein:

图1a、1b、1c是根据本发明的层压包装材料的横截面视图；Figures 1a, 1b, 1c are cross-sectional views of a laminated packaging material according to the invention;

图2a、2b、2c是在图1所示的对应层压包装材料制造的方法的示意图；和Figures 2a, 2b, 2c are schematic diagrams of the method of manufacture of the corresponding laminated packaging material shown in Figure 1; and

图3是传统的结构稳定的包装容器的透视侧立视图，该包装容器由本发明的层压的包装材料制成。Figure 3 is a perspective side elevation view of a conventional structurally stable packaging container made from the laminated packaging material of the present invention.

优选实施例的详细描述Detailed description of the preferred embodiment

参见图1a，它是根据本发明的优选的层压包装材料10a的横截面视图。包装材料10a包括纸或纸板的刚性结构但可折叠的芯层11。在芯层11的一侧上，涂敷有聚酰胺混合物的阻气层12，该聚酰胺混合物包含尼龙-MXD6和PA-6或最好是基于PA-6的尼龙粘土混合物(NCH)。在聚酰胺混合物内的尼龙-MXD6的量以重量百分比计较好是混合物的60-90％，最好是70-80％，在阻气层内的聚酰胺混合物的量最好是5-10克/米²。See Figure 1a, which is a cross-sectional view of a preferred laminated packaging material 10a according to the present invention. The packaging material 10a comprises a rigid structural butfoldable core layer 11 of paper or cardboard. On one side of thecore layer 11, agas barrier layer 12 of a polyamide mixture comprising nylon-MXD6 and PA-6 or preferably a nylon-clay mixture (NCH) based on PA-6 is applied. The amount of nylon-MXD6 in the polyamide mixture is preferably 60-90% of the mixture in terms of weight percentage, preferably 70-80%, and the amount of the polyamide mixture in the gas barrier layer is preferably 5-10 grams /^m2 .

包括尼龙-MXD6和PA-6或NCH的混合物的阻气层12经证实很好的粘合到纸或纸板的芯层11上。与将聚乙烯的中间层与芯层11上的阻气层12层压相比，已经证实阻气层12直接设置在芯层11上导致阻氧性提高30-40％的阻挡氧气层。Agas barrier layer 12 comprising a blend of nylon-MXD6 and PA-6 or NCH has proven to adhere well to thecore layer 11 of paper or paperboard. Compared to laminating an interlayer of polyethylene with thegas barrier layer 12 on thecore layer 11, it has been demonstrated that the direct placement of thegas barrier layer 12 on thecore layer 11 results in an oxygen barrier layer with 30-40% improved oxygen barrier properties.

在阻气层12的一侧，该阻气层12转到面朝离开芯层11，涂敷聚烯烃层13，该聚烯烃层13通过粘附到阻气层12和聚烯烃层13之间的粘合剂聚合物层14粘合到阻气层12上。聚烯烃层13最好是LDPE或m-PE或其混合物，并最好以至少25克/米²的量涂敷。粘合层14由聚乙烯接枝组成并以约3-6克/米²的量涂敷，该聚乙烯接枝由顺丁烯二酸酐改性。在芯层的相对侧上的外层15最好类似的是LDPE或m-PE，或这两种聚合物的混合物，并最好以至少15克/米²的量涂敷。On one side of thegas barrier layer 12, which is turned to face away from thecore layer 11, a polyolefin layer 13 is applied which is bonded between thegas barrier layer 12 and the polyolefin layer 13 The adhesive polymer layer 14 is bonded to thegas barrier layer 12. The polyolefin layer 13 is preferably LDPE or m-PE or a mixture thereof and is preferably applied in an amount of at least 25 g/^m2 . The adhesive layer 14 consists of a polyethylene graft modified with maleic anhydride and is applied in an amount of about 3-6 g/^m2 . The outer layer 15 on the opposite side of the core layer is preferably similarly LDPE or m-PE, or a mixture of these two polymers, and is preferably applied in an amount of at least 15 g/^m2 .

参见图1b，它表示根据本发明的另一种优选的层压包装材料10b的横截面图。包装材料10b包括纸或纸板的结构刚性但可折叠的芯层11。在芯层11的一侧，涂敷有包含尼龙-MXD6和PA-6或最好是基于PA-6的尼龙粘土混合物(NCH)的聚酰胺混合物的阻气层12。在聚酰胺混合物内的尼龙-MXD6的量以重量百分比计较好是混合物的60-90％，最好是70-80％，在阻气层内的聚酰胺混合物的量最好是5-10克/米²。Referring to Figure 1b, there is shown a cross-sectional view of another preferred laminated packaging material 10b according to the present invention. The packaging material 10b comprises a structurally rigid butfoldable core layer 11 of paper or paperboard. On one side of thecore layer 11, agas barrier layer 12 comprising a polyamide mixture of nylon-MXD6 and PA-6 or preferably a nylon-clay mixture (NCH) based on PA-6 is applied. The amount of nylon-MXD6 in the polyamide mixture is preferably 60-90% of the mixture in terms of weight percentage, preferably 70-80%, and the amount of the polyamide mixture in the gas barrier layer is preferably 5-10 grams /^m2 .

在阻气层12的一侧，该阻气层12转到面朝离开芯层11，涂敷聚烯烃层13，该聚烯烃层13通过粘附到阻气层12和聚烯烃层13之间的粘合剂聚合物层14粘合到阻气层12上。聚烯烃层13最好是LDPE或m-PE或其混合物，并最好以至少25克/米²的量涂敷。粘合层14由聚乙烯接枝组成并以约3-6克/米²的量涂敷，该聚乙烯接枝由顺丁烯二酸酐改性。在芯层的相对侧上的外层15最好类似的是LDPE或m-PE，或这两种聚合物的混合物，并最好以至少15克/米2的量涂敷。On one side of thegas barrier layer 12, which is turned to face away from thecore layer 11, a polyolefin layer 13 is applied which is bonded between thegas barrier layer 12 and the polyolefin layer 13 The adhesive polymer layer 14 is bonded to thegas barrier layer 12. The polyolefin layer 13 is preferably LDPE or m-PE or a mixture thereof and is preferably applied in an amount of at least 25 g/^m2 . The adhesive layer 14 consists of a polyethylene graft modified with maleic anhydride and is applied in an amount of about 3-6 g/^m2 . The outer layer 15 on the opposite side of the core layer is preferably similarly LDPE or m-PE, or a mixture of these two polymers, and is preferably applied in an amount of at least 15 g/m2.

阻气层12通过粘合聚合物层16和聚乙烯层17的中间粘合层粘合到芯层上，粘合聚合物层16靠近阻气层12，并与粘合聚合物层14具有相同的聚合物和几乎相同的厚度，且聚乙烯层17与层13的聚合物相同，并且厚度几乎相同。Thegas barrier layer 12 is bonded to the core layer through an intermediate adhesive layer of anadhesive polymer layer 16 and apolyethylene layer 17, theadhesive polymer layer 16 is adjacent to thegas barrier layer 12 and has the same properties as the adhesive polymer layer 14. The polymer and almost the same thickness, and thepolyethylene layer 17 is the same polymer as layer 13, and the thickness is almost the same.

参见图1C，它表示根据本发明的另一种优选的层压包装材料10c的横截面图。包装材料10c包括纸或纸板的刚性结构但可折叠的芯层11。芯层11的一侧上，涂敷有第一阻气层12和第二阻气层12’，这两种阻气层基本上由尼龙-MXD6和PA-6或最好是基于PA-6的尼龙粘土混合物(NCH)的聚酰胺混合物构成。在聚酰胺混合物中的尼龙-MXD-6的量以重量百分比计较好的是混合物的60-90％，最好是70-80％，在阻气层中的聚酰胺混合物的量最好是5-10克/米²。Referring to Figure 1C, there is shown a cross-sectional view of another preferredlaminated packaging material 10c according to the present invention. Thepackaging material 10c comprises a rigid structural butfoldable core layer 11 of paper or cardboard. On one side of thecore layer 11, a firstgas barrier layer 12 and a second gas barrier layer 12' are coated, and these two gas barrier layers are basically made of nylon-MXD6 and PA-6 or preferably based on PA-6 Constructed of nylon clay mixture (NCH) polyamide mixture. The amount of nylon-MXD-6 in the polyamide mixture is preferably 60-90% of the mixture in weight percent, preferably 70-80%, and the amount of the polyamide mixture in the gas barrier layer is preferably 5% -10 g/^m2 .

在面朝离开芯层11的阻气层12的一侧，涂敷聚烯烃13’，该聚烯烃13’通过在阻气层12和聚烯烃13’之间涂敷的粘合剂聚合物层14来粘合到阻气层12上。聚烯烃13’最好是LDPE或m-PE，或其混合物，并涂敷最好至少15-20克/米²的量。粘合层14由聚乙烯接枝组成并以约3-6克/米²的量涂敷，该聚乙烯接枝由顺丁烯二酸酐改性。在芯层的相对侧上的外层15最好类似的是LDPE或m-PE，或这两种聚合物的混合物，并最好以至少15-20克/米²的量涂敷。On the side of thegas barrier layer 12 facing away from thecore layer 11, a polyolefin 13' is applied, which is passed through an adhesive polymer layer applied between thegas barrier layer 12 and the polyolefin 13' 14 to be bonded to thegas barrier layer 12. The polyolefin 13' is preferably LDPE or m-PE, or mixtures thereof, and is preferably applied in an amount of at least 15-20 g/^m2 . The adhesive layer 14 consists of a polyethylene graft modified with maleic anhydride and is applied in an amount of about 3-6 g/^m2 . The outer layer 15 on the opposite side of the core layer is preferably similarly LDPE or m-PE, or a mixture of these two polymers, and is preferably applied in an amount of at least 15-20 g/^m2 .

在聚乙烯层13’的一侧，该聚乙烯层13’转到面朝离开芯层11，第二阻挡气体和味道层12’通过粘合聚合物层16’和聚乙烯层17’的中间粘合层涂敷。或者，在一次挤压操作中所有层的共挤的情况下，聚乙烯层13’和17’实际上作为一个单层涂敷。On the side of the polyethylene layer 13' which is turned to face away from thecore layer 11, the second gas and taste barrier layer 12' is passed between the adhesive polymer layer 16' and the polyethylene layer 17' Adhesive coating. Alternatively, in the case of coextrusion of all layers in one extrusion operation, the polyethylene layers 13' and 17' are actually applied as a single layer.

在面朝离开芯层11的阻气层12’的一侧，涂敷最内的聚烯烃层18，该聚烯烃层18通过粘附到阻气层12’和聚烯烃层18之间的粘合聚合物层14’粘合到阻气层12’。最内的聚乙烯层18应较薄，以防止太多的芳香和味道物质从包装好的产品溢出到包装材料内。较好的是该层应以约6-12克/米²的量，更好的是最大以10克/米²的量，最好以约7-9克/米²的量涂敷。On the side facing the gas barrier layer 12' away from thecore layer 11, aninnermost polyolefin layer 18 is applied, which is adhered to the gas barrier layer 12' and thepolyolefin layer 18 through the adhesive bond between the gas barrier layer 12' and thepolyolefin layer 18. The composite polymer layer 14' is bonded to the gas barrier layer 12'. Theinnermost polyethylene layer 18 should be relatively thin in order to prevent too much aroma and taste substances from escaping from the packaged product into the packaging material. Preferably the layer should be applied in an amount of about 6-12 g/^m2 , more preferably a maximum of 10 g/^m2 , most preferably about 7-9 g/^m2 .

粘合剂层16’和14’包括与粘合剂聚合物层14相同的聚合物，并应具有3-5最好4克/米²的厚度，而聚乙烯层17’包括相同的聚合物，并具有与最内的聚乙烯层18几乎相同的厚度。Adhesive layers 16' and 14' comprise the same polymer as adhesive polymer layer 14 and should have a thickness of 3-5 preferably 4 g/m² while polyethylene layer 17' comprises the same polymer , and has almost the same thickness as theinnermost polyethylene layer 18.

图1C的层压的包装材料的优点是，在层压制品内部的薄聚烯烃层14’和18以及阻挡气体和芳香层12’一起防止非极性物质从包装好的产品迁移入包装材料内，因为薄聚烯烃层不久由该物质浸透，且阻挡层12’有效地阻挡向包装层压制品的内部的所有其它迁移。An advantage of the laminated packaging material of FIG. 1C is that the thin polyolefin layers 14' and 18 inside the laminate together with the gas barrier and fragrance layer 12' prevent the migration of non-polar substances from the packaged product into the packaging material. , since the thin polyolefin layer is soon saturated by the substance and the barrier layer 12' effectively blocks all other migrations towards the interior of the packaging laminate.

层压制品的密封性能仍然极佳，因为中间聚烯烃层13’和17’以及粘合层16’提供大部分可热密封聚合物，该可热密封聚合物补偿在最内的聚乙烯层18中损失的可热密封聚合物的量。在沿密封区加热和加压时，阻挡层12’变得“密封透”，这样在热熔密封操作中包含大部分层13’和17’。The sealing properties of the laminate are still excellent because the middle polyolefin layers 13' and 17' and the adhesive layer 16' provide the majority of the heat-sealable polymer which compensates for theinnermost polyethylene layer 18 The amount of heat-sealable polymer lost in the Upon application of heat and pressure along the sealing zone, the barrier layer 12' becomes "seal through", thus encompassing most of the layers 13' and 17' during the heat-melt sealing operation.

通过采用尼龙-MXD6和PA-6或最好是NCH的聚酰胺混合物的两个阻气层，将进一步改进阻气性。而且，层压制品的刚度将变高，因为聚酰胺层的相对刚度和它们相互距离为低刚性材料层(导致所谓的I梁效果的危险)，这会改善包装的外观，或者甚至有可能使用低刚性质量的芯层。因此，在这种层压制品中，鼓胀的效果将很少看到，因为包装层压制品具有较高的总刚度。The gas barrier properties will be further improved by using two gas barrier layers of a polyamide blend of nylon-MXD6 and PA-6 or preferably NCH. Also, the stiffness of the laminate will become higher due to the relative stiffness of the polyamide layers and their mutual distance to the layers of less stiff material (leading to the danger of the so-called I-beam effect), which improves the appearance of the package, or it is even possible to use Core layer with low rigid mass. Therefore, in such laminates, the effect of bulging will be less seen due to the higher overall stiffness of packaging laminates.

图2a示意性表示制造图1a的层压包装材料的方法。Figure 2a schematically represents a method of manufacturing the laminated packaging material of Figure 1a.

纸板衬底芯层11的网向前，并穿过表面激活台21，这里表面通过电晕和/或火焰处理最好是火焰处理得以激活。通过在进给机22中产生三层膜，层12，13和14以所述顺序共挤22。膜24穿过模具和纸板衬底之间的气隙供送给模具23。指向纸板表面的表面层12最好通过暴露到臭氧处理25中的气隙内激活处理。共挤过和仍热的熔化的多层膜24与纸板网一起供给通过辊隙26，这样通过聚合物层的压力和热导致粘合。重要的是共挤聚合物的量足够高，以保持足够温热，直到它与纸板衬底接触为止。如果三层12，13和14是一起共挤到网上，这是一般的情况。然而，例如仅有层12和14的共挤不具备优点，因为两层共挤膜非常迅速的冷却，而且不会温热到能够良好的粘合到纸网26。The web ofpaperboard substrate core 11 is advanced and passed through asurface activation station 21 where the surface is activated by corona and/or flame treatment, preferably flame treatment.Layers 12 , 13 and 14 are coextruded 22 in the sequence described by creating a three-layer film infeeder 22 . Thefilm 24 is fed to themold 23 through the air gap between the mold and the paperboard substrate. Thesurface layer 12 directed toward the paperboard surface is preferably treated by in-air activation by exposure to an ozone treatment 25 . The coextruded and still hotmolten multilayer film 24 is fed through a nip 26 with the paperboard web so that pressure and heat through the polymer layers cause bonding. It is important that the amount of coextruded polymer is high enough to remain warm enough until it comes into contact with the paperboard backing. This is generally the case if the threelayers 12, 13 and 14 are coextruded together onto the web. However, coextrusion of only layers 12 and 14, for example, does not offer advantages because the two-layer coextruded film cools very rapidly and is not warm enough to bond to thepaper web 26 well.

聚烯烃层15可通过挤压涂布从而涂布在芯层的一侧上，在图2a所示的共挤涂布方法之前或之后，该芯层转到朝向离开阻气层12。The polyolefin layer 15 can be coated by extrusion coating on one side of the core layer which is turned towards away from thegas barrier layer 12 before or after the co-extrusion coating process shown in Fig. 2a.

图2b示意性表示图1b的层压包装材料的制造方法。Fig. 2b schematically shows a method of manufacturing the laminated packaging material of Fig. 1b.

如图1a所示，除了在芯层11上的所述三层结构外，还有可能在不脱离本发明的范围前提下，提供包括四和五层与芯层11层压到一起的层压结构。四层结构具有在芯层和阻气层12之间的粘合接触层。在五层结构的情况下，如图1b所示，聚烯烃层17以及粘合层16涂布在芯层11和阻气层12之间，然后聚烯烃层17布置成靠近芯层11。然而，这些多层结构成本更高的制造，因为消耗更多的材料量。与图2a所述的制造三层结构的工艺相比，该工艺仍非环境良好(很少的资源减少)，且消耗更多的能量。As shown in Figure 1a, in addition to the described three-layer structure on thecore layer 11, it is also possible to provide laminates comprising four and five layers laminated together with thecore layer 11 without departing from the scope of the present invention. structure. The four-layer structure has an adhesive contact layer between the core layer and thegas barrier layer 12 . In the case of a five-layer structure, as shown in FIG. 1 b , apolyolefin layer 17 and anadhesive layer 16 are coated between thecore layer 11 and thegas barrier layer 12 , and then thepolyolefin layer 17 is arranged close to thecore layer 11 . However, these multilayer structures are more expensive to manufacture because of the greater amount of material consumed. This process is still not environmentally friendly (little resource reduction) and consumes more energy than the process described in Fig. 2a for making a three-layer structure.

最好，以与图2a类似的方式，图1b的层压制品通过五层12、13、14、16和17共挤到纸板网11上来制造。纸板衬底芯层11的网向前，并穿过表面激活台21，在此，表面通过电晕和/或火焰处理激活。层17、16、12、14和13以所述顺序共挤22，这样提供经过模具23的多层膜24’，层17指向纸板表面。共挤过和仍热的熔化多层膜24’最好通过臭氧25进行表面激活处理，然后与纸板网一起供给通过辊隙26，这样通过聚合物层的压力和热粘合到一起。Preferably, the laminate of Figure 1b is produced by coextrusion of the fivelayers 12, 13, 14, 16 and 17 onto thepaperboard web 11 in a similar manner to that of Figure 2a. The web ofpaperboard substrate core 11 is forwarded and passed through asurface activation station 21 where the surface is activated by corona and/or flame treatment.Layers 17, 16, 12, 14 and 13 are coextruded 22 in the order described, thus providing a multilayer film 24' passing through die 23 withlayer 17 directed towards the paperboard surface. The coextruded and still hot fused multilayer film 24' is preferably surface activated by ozone 25 and then fed through thenip 26 with the paperboard web so that it is bonded together by the pressure and heat of the polymer layers.

另一种方式，在芯层11内部的五层可以两个步骤涂敷，即通过在第一步骤首先将层17、16、12和14共挤到纸板上，然后在第二步骤将层13挤压涂布在层14上，或者通过在第一步骤首先将层17挤压到芯层上，然后，在第二步骤将四层16、12、14和13共挤到新涂敷的层17上。然而，这些替代方法包含更繁琐和低成本效率的工艺。Alternatively, the five layers inside thecore layer 11 can be applied in two steps, by first coextruding layers 17, 16, 12 and 14 onto paperboard in a first step, and then layer 13 in a second step. Extrusion coating on layer 14, either by first extrudinglayer 17 onto the core layer in a first step and then coextruding the fourlayers 16, 12, 14 and 13 onto the freshly applied layer in asecond step 17 on. However, these alternative methods involve more cumbersome and cost-effective processes.

在图2b所示的共挤涂布方法之前或之后，聚烯烃层15可通过挤压涂布在芯层的一侧上来涂敷，该芯层转到面朝离开阻气层12。Before or after the coextrusion coating method shown in FIG. 2 b , the polyolefin layer 15 can be applied by extrusion coating on one side of the core layer, which turns to face away from thegas barrier layer 12 .

图2c示意性表示图1c的层压包装材料的制造方法。Fig. 2c schematically shows a method of manufacturing the laminated packaging material of Fig. 1c.

根据一个实施例，对于可获得七层进给机的情况，以与图2a和2b类似的方式，图1c的层压制品通过将七层12、14、13’+17’、16’、12’、14’和18共挤到纸板网11上来制造。According to one embodiment, for the case where a seven-layer feeder is available, in a similar manner to FIGS. 2a and 2b, the laminate of FIG. ', 14' and 18 are co-extruded onto thecardboard web 11 to manufacture.

根据一个优选实施例，在第一步骤中，层12、14和13’共挤涂布到纸板网上，在第二步骤中，层17’、16’、12’、14’和18共挤涂布到层13’上。这样，纸板衬底芯层11的网向前并穿过表面激活台21，在此表面由电晕和/或最好是火焰处理来激活。层12、14和13以所述顺序共挤在进给机22内，产生三层膜24”，该三层膜24”经过模具23供送到模具和纸板衬底之间的气隙。多层膜24”的层12指向纸板表面。就在与纸网接触之前，层12的表面最好由臭氧处理25进行预处理。共挤过和仍热的熔化的臭氧处理多层膜24”与纸板网一起经过辊隙26供送，这样，通过聚合物层的压力和热粘合到一起。According to a preferred embodiment, in a first step layers 12, 14 and 13' are coextruded onto a cardboard web and in a second step layers 17', 16', 12', 14' and 18 are coextrusion coated Clothed onto layer 13'. Thus, the web ofpaperboard substrate core 11 is advanced and passed throughsurface activation station 21 where the surface is activated by corona and/or preferably flame treatment.Layers 12, 14 and 13 are co-extruded in the sequence described infeeder 22, resulting in a three-layer film 24", which is fed through die 23 into the air gap between the die and the paperboard substrate.Layer 12 ofmultilayer film 24" is directed toward the paperboard surface. The surface oflayer 12 is preferably pretreated by ozone treatment 25 just prior to contact with the paper web. Coextruded and still hot molten ozone treatedmultilayer film 24" The paperboard web is fed through thenip 26 so that it is bonded together by pressure and heat of the polymer layers.

在第二步骤中，层17’、16’、12’、14’和18共挤涂布22’到在第一步骤制成的层压制品上，例如五层膜24。或者，只有四层16’、12’、14’和18的多层膜挤压到在第一步骤制成的层压制品上。共挤过和仍热的，熔化的多层膜24由臭氧可选择的表面激活处理，并与涂布的纸板网11’一起经过辊隙26’供送，这样，通过聚合物层的压力和热粘合到一起。In a second step, thelayers 17', 16', 12', 14' and 18 are coextruded 22' onto the laminate made in the first step, for example a five-layer film 24''. Alternatively, a multilayer film of only fourlayers 16', 12', 14' and 18 is extruded onto the laminate produced in the first step. The coextruded and still hot, molten multilayer film 24'' is optionally surface-activated by ozone and is fed through the nip 26' together with the coated paperboard web 11' so that, through the pressure of the polymer layer and hot glued together.

在图2c所示的共挤涂布方法之前或之后，聚烯烃层15可通过挤压涂布涂敷到芯层的侧面上，该芯层转到面朝离开阻气层12。Before or after the co-extrusion coating method shown in FIG. 2 c , the polyolefin layer 15 can be applied by extrusion coating onto the side of the core layer which is turned to face away from thegas barrier layer 12 .

从根据本发明的层压好的包装材料10看，具有良好阻挡氧气性能的液密的、尺寸稳定的包装30可利用公知的包装和填充设备制造，该设备在连续工艺中将填充和密封的板形或网形包装材料形成完成的包装30。这种传统的包装容器的一个例子如图3所示。From the laminated packaging material 10 according to the present invention, a liquid-tight, dimensionallystable package 30 with good oxygen barrier properties can be manufactured using known packaging and filling equipment that combines filled and sealed packaging in a continuous process. The packaging material in sheet or web form forms thefinished package 30 . An example of such a conventional packaging container is shown in FIG. 3 .

根据本发明的包装容器可设有打开装置31，这种打开/关闭装置通常在液体食物包装中公知。The packaging container according to the invention can be provided with opening means 31, such opening/closing means are generally known in liquid food packaging.

将层压包装材料转化成包装容器的工艺例如通过首先使网形层压包装材料10的纵边卷成一个管，该管内填充有想要的包含物，这样来实施该工艺，然后，通过在包含物水平下方的管的重复横向密封，使单个的包装30分开。通过最终的折叠成形和密封工艺，包装30通过在横向密封区内的切口相互分离，并获得理想的几何外形，通常平行管。或者，包装30的形成可通过将板折叠成形为纸箱坯料，然后填充和封闭该坯料以形成完成的包装来完成。The process of converting the laminated packaging material into a packaging container is carried out, for example, by first rolling the longitudinal sides of the web-shaped laminated packaging material 10 into a tube filled with desired inclusions, and then by Repeated transversal sealing of the tube below the level of contents separates the individual packages 30 . Through the final folding forming and sealing process, thepackages 30 are separated from each other by incisions in the transversal sealing zone and obtain a desired geometric shape, generally parallel tubes. Alternatively, forming thepackage 30 may be accomplished by folding and forming a panel into a carton blank, then filling and closing the blank to form the finished package.

对本领域的普通技术人员来说，显然本发明不仅限于图示的实施例，在不超出本发明的由附属的权利要求书限定的范围的前提下，可做许多不同的修改和变化。例如，图1所示的材料结构通常不限于图示数量层，该数量可大可小，但可响应包装材料的理想用途自由变换。It is obvious to those skilled in the art that the present invention is not limited to the illustrated embodiments, and that many different modifications and changes can be made without departing from the scope of the present invention defined by the appended claims. For example, the material structure shown in Figure 1 is generally not limited to the number of layers shown, which may be greater or lesser, but may be freely varied in response to the desired use of the packaging material.

实例example

实例1Example 1

阻挡层性能的对比：不同的聚酰胺阻氧层Comparison of Barrier Properties: Different Polyamide Oxygen Barriers

针对完全的包装材料结构进行测量，即共挤5层结构(克/米²)：Measured for the complete packaging material structure, i.e. a co-extruded 5-layer structure (g/^m2 ):

LDPE(13)/板/LDPE(10)/复合薄膜粘结层(5)/PA(阻挡层)(6)/复合薄膜粘结层(5)/LDPE(25)LDPE(13)/board/LDPE(10)/composite film adhesive layer(5)/PA(barrier layer)(6)/composite film adhesive layer(5)/LDPE(25)

阻挡层涂敷重量：分别是6和10克/米²Barrier coating weight: 6 and 10 g/^m2 respectively

PA6：UBE工业中标准PA-6 1024B等级PA6: Standard PA-6 1024B grade in UBE industry

Selar PA3508：非晶态聚酰胺Selar PA3508: Amorphous polyamide

当在阻气层中单独使用时，PA6的氧气渗透值是约与在0％RH时的Selar聚酰胺一样高，但在较高相对湿度下较高。作为单独的阻气层，Selar PA或PA6对ESL包装经济上不重要。When used alone in the gas barrier layer, the oxygen permeability value of PA6 is about as high as Selar polyamide at 0% RH, but higher at higher relative humidity. As a separate gas barrier layer, Selar PA or PA6 is not economically important for ESL packaging.

测试方法：“Mocon oxtran“，1000平试样方法，试验气体：100％氧，T＝23℃，t＝24h，RH：50％，1atm，n(样品数)＝5Test method: "Mocon oxtran", 1000 flat sample method, test gas: 100% oxygen, T=23°C, t=24h, RH: 50%, 1atm, n (number of samples)=5

表1 在阻挡层中的聚酰胺等级渗透性(cc/m²)6g/m² 渗透性(cc/m²)10g/m² Selar(a)PA3508 80.1cc/m² 58.3cc/m² 60％MXD6/40％PA6 50.4cc/m² 26.3cc/m² 60％MXD6/40％PA6-NCH(1022CM1) 29.6cc/m² 22.6cc/m² 80％MXD6/20％PA6 33.3cc/m² 19.8cc/m² 100％MXD6 -- 14.6cc/m²Table 1 Polyamide grades in barrier layers Permeability (cc/m² )6g/m² Permeability (cc/m² )10g/m² Selar(a)PA3508 80.1cc/^m2 58.3cc/^m2 60% MXD6/40% PA6 50.4cc/^m2 26.3cc/^m2 60% MXD6/40% PA6-NCH (1022CM1) 29.6cc/^m2 22.6cc/^m2 80% MXD6/20% PA6 33.3cc/^m2 19.8cc/^m2 100% MXD6 -- 14.6cc/^m2

结论：尼龙-MXD6/PA6的混合物具有比非晶态PA好的阻氧性。具有尼龙粘土混合物-PA6的尼龙-MXD6混合物具有比相应的具有标准PA6等级的尼龙-MXD6混合物好的阻氧性。尽管对于具有100％尼龙-MXD6阻气层的层压制品来说，已经获得阻气值，这种层压制品实际上不可使用，因为阻气层将破裂并分层，并允许氧气渗入其制成的包装容器中。具有重量百分比为80％尼龙-MXD6的尼龙-MXD6混合物具有比对应的重量百分比为60％的混合物高的阻氧性。尽管在这些实际的例子中，已经发现通过其它试验可知在由层压制品制成的包装中，在混合物中重量百分比为约70％-80％时可获得在阻气性和力学性能之间的最佳平衡。在大于重量百分比为90％的尼龙-MXD6时，阻挡层变得更脆和不可弯曲，这样更易于破裂和分层。Conclusion: The mixture of nylon-MXD6/PA6 has better oxygen barrier than amorphous PA. Nylon-MXD6 blends with nylon clay blend-PA6 have better oxygen barrier properties than corresponding nylon-MXD6 blends with standard PA6 grades. Although gas barrier values have been obtained for laminates with a 100% Nylon-MXD6 gas barrier layer, such laminates are practically unusable because the gas barrier layer will crack and delaminate and allow oxygen to penetrate into its into the finished packaging container. A nylon-MXD6 blend having 80% by weight nylon-MXD6 has a higher oxygen barrier than a corresponding blend having 60% by weight. Although in these practical examples, it has been found by other experiments that in packages made of laminates, a balance between gas barrier and mechanical properties can be obtained at about 70%-80% by weight in the mixture. optimal balance. At greater than 90% by weight nylon-MXD6, the barrier layer becomes more brittle and inflexible, which is more prone to cracking and delamination.

例子2Example 2

尼龙-MXD6聚酰胺混合物的混合物质量：Blend Quality of Nylon-MXD6 Polyamide Blend:

在尼龙-MXD6/PA6-混合物混合时的不同的熔化温度的影响Effect of Different Melting Temperatures on Mixing of Nylon-MXD6/PA6-Blends

为了获得两相不混溶的混合物，即在DSC测量时具有两个熔点或熔化间隔的混合物，聚合物应在低熔化温度，较短的混合时间和混合时使用低剪切的条件下混合。实际上，不同的聚合物颗粒干燥混合，然后在一个挤压机内熔化混合，与此同时将聚合物供送到挤压模中。两相混合物提供比单相混合物好的阻氧性。In order to obtain a two-phase immiscible mixture, i.e. a mixture with two melting points or melting intervals as measured by DSC, the polymers should be mixed at low melting temperatures, short mixing times and low shear during mixing. In practice, pellets of different polymers are dry-blended and then melt-blended in an extruder while the polymers are being fed into extrusion dies. Two-phase mixtures provide better oxygen barrier than single-phase mixtures.

在具有相同的挤压设备和模具时的小规模试验中进行下列观察。在挤压单层膜(200+10％微米)时进行氧渗透试验。The following observations were made in a small scale test with the same extrusion equipment and dies. Oxygen permeation tests were performed on extruded monolayer films (200+10% microns).

方法：Mocon oxtran，1000平试样法，试验气体：100％氧，T＝23℃，t＝24h，RH：50％，1atm，n(样品数)＝5Method: Mocon oxtran, 1000 flat sample method, test gas: 100% oxygen, T=23°C, t=24h, RH: 50%, 1atm, n (number of samples)=5

表2 PA混合物熔化温度氧渗透性 60％MXD6/40％PA6-NCH 290℃ 1.25cc/m² 60％MXD6/40％PA6-NCH 270℃ 0.43cc/m²Table 2 PA mixture melting temperature oxygen permeability 60% MXD6/40% PA6-NCH 290°C 1.25cc/^m2 60% MXD6/40% PA6-NCH 270°C 0.43cc/^m2

结论：与具有高熔化混合物温度的膜相比，在较低的混合物熔化温度下制成的膜具有大于100％的更好的阻氧性，这表示在较高温度下的混合提供更易混合型混合物。Conclusions: Films made at lower blend melting temperatures had greater than 100% better oxygen barrier properties than films with high melting blend temperatures, indicating that blending at higher temperatures provided a more miscible form mixture.

例子3Example 3

阻挡性的比较：3层与5层结构比较Comparison of barrier properties: comparison of 3-layer and 5-layer structures

测量大规模共挤涂布制成的材料的完整的包装材料结构Measuring the complete packaging material structure of materials produced by large-scale coextrusion coating

5层结构(g/m²)：5-layer structure (g/m² ):

LDPE(16)/板/LDPE(15)/复合薄膜粘结层(5)/PA-混合物(7)/复合薄膜粘结层(5)/LDPE(20)LDPE(16)/board/LDPE(15)/composite film tie layer(5)/PA-blend(7)/composite film tie layer(5)/LDPE(20)

3层结构(g/m²)：3-layer structure (g/m² ):

LDPE(16)/板/PA-混合物(7)/复合薄膜粘结层(5)/LDPE(20)LDPE(16)/board/PA-blend(7)/composite film adhesive layer(5)/LDPE(20)

聚酰胺混合物：7g/m²，75％MXD6+25％PA6-NCHPolyamide blend: 7g/m² , 75% MXD6+25% PA6-NCH

方法：Mocon oxtran，1000平试样法，试验气体：21％氧，T＝23度，t＝24h，RH：80％，1atm，n(样品数)＝2Method: Mocon oxtran, 1000 flat sample method, test gas: 21% oxygen, T=23 degrees, t=24h, RH: 80%, 1atm, n (number of samples)=2

表3 结构氧渗透性第一值第二值 5层 28.9cc/g/m² 28.3cc/g/m² 3层 20.2cc/g/m² 20.9cc/g/m²table 3 structure oxygen permeability first value second value 5th floor 28.9cc/g/^m2 28.3cc/g/^m2 3 floors 20.2cc/g/^m2 20.9cc/g/^m2

结论：3层结构比5层结构具有40％更好的阻氧性。Conclusion: The 3-layer structure has 40% better oxygen barrier than the 5-layer structure.

例子4Example 4

在外聚乙烯层的克数之间的重量比的效果The effect of the weight ratio between the grams of the outer polyethylene layer

在10周冷藏后在两个单独的试验中测量到鼓胀，每个试验包括充满橙汁的10个包装物，在包装容器壁之间的宽度的mm数超过76mm。在表中给出的值是超过或落在具有LDPE(16)/板/LDPE(15)/复合薄膜粘结层(5)/PA-混合物(7)/复合薄膜粘结层(5)/LDPE(20)结构(g/m²)的参考包装的值之下。Bulging was measured in two separate experiments, each involving 10 packages filled with orange juice, after 10 weeks of refrigeration, the width in mm between the packaging container walls exceeding 76mm. The values given in the table are above or below those with LDPE(16)/board/LDPE(15)/composite film tie layer(5)/PA-blend(7)/composite film tie layer(5)/ Below the value of the reference package for LDPE (20) structure (g/m² ).

具有75∶25尼龙-MXD6混合物与PA6 NCH的阻气层的类似结构具有几乎与EVOH参考样品(在其它试验中测量的)相同的鼓胀性。A similar structure with a gas barrier layer of 75:25 nylon-MXD6 blend and PA6 NCH had almost the same swell as the EVOH reference sample (measured in other tests).

在根据ASTM D4729-D4169D 随机变化试验之后测量泄漏频率，层叠的随机变化实施15分钟n(包装数)＝160Leakage frequency is measured after random variation test according to ASTM D4729-D4169D, stacked random variation is implemented for 15 minutes n(number of packages)=160

层压试验(g/m²)Lamination test (g/m² )

LDPE(16)/75∶25MXD6∶PA6NCH(6)/复合薄膜粘结层(3)//LDPE(X)LDPE(16)/75:25MXD6:PA6NCH(6)/composite film adhesive layer(3)//LDPE(X)

表4A：泄漏编号最内层的总量g/m² 在内部的聚合物g/m² 外部g/m² 泄漏频率(每160包装的包装数)密封强度 1a 20 29 16 46 2a 25 34 16 20 3a 30 39 16 8Table 4A: Leakage serial number The total amount of the innermost layer g/m² Polymer inside g/m² External g/m² Leakage Frequency (Packs per 160 Packs) Seal Strength 1a 20 29 16 46 2a 25 34 16 203a 30 39 16 8

结论：当在纸板内侧上的聚合物量(阻挡层+粘结层+LDPE)高时，发生极少的泄漏。Conclusion: Very little leakage occurs when the amount of polymer (barrier + tie + LDPE) on the inside of the board is high.

表4B：鼓胀编号最内层g/m² 总内部外部与样品相比的鼓胀 1a 20 29 16 +2mm 1b 20 -- 2a 25 34 16 0mm 2b 20 +2mm 3a 30 39 16 -2mm 3b 20 0mmTable 4B: Bulging serial number Innermost layer g/m² total interior external Swelling compared to sample 1a 20 29 16 +2mm 1b 20 -- 2a 25 34 16 0mm 2b 20 +2mm 3a 30 39 16 -2mm 3b 20 0mm

结论：当外侧上的聚合物量低且内侧上的量高时，鼓胀减少。Conclusions: When the amount of polymer on the outside is low and the amount on the inside is high, bulging is reduced.

为了在与参考的五层层压制品具有相同或较低的水平下保持三层层压制品的鼓胀水平，在最内侧的LDPE量必须至少为25g/m²，最好至少为30g/m²。LDPE层的外侧应小于20g/m²，最好约为16g/m²。在16g/m²之下，外侧装饰层的适印性可削弱。In order to maintain the bulging level of the three-layer laminate at the same or lower level than the reference five-layer laminate, the amount of LDPE on the innermost side must be at least 25 g/m² , preferably at least 30 g/m² . The outer side of the LDPE layer should be less than 20 g/m² , preferably about 16 g/m² . Below 16 g/m² , the printability of the outer decorative layer may be impaired.

鼓胀结果表明通过在恒定的外侧层涂敷厚的内侧层，产生很少的鼓胀。然而，不希望的是，当内侧量保持较高，而外侧量保持较低时，与五层参考样品相比三层结构表现出很低的鼓胀，这是不期望的和令人惊奇的，因为在五层纸板层压制品内侧上的阻挡液体聚烯烃的量较高，即共45g/m²，(在五层层压制品内的总内侧聚合物为50g/m²)。Bulging results show that by coating a thick inner layer over a constant outer layer, little bulging occurs. However, when the inner volume is kept higher and the outer volume is kept low, the three-layer structure exhibits very low bulging compared to the five-layer reference sample, which is not expected and surprising, Because the amount of barrier liquid polyolefin on the inside of the five-ply paperboard laminate is higher, ie a total of 45 g/m² , (total inside polymer in the five-ply laminate is 50 g/m² ).